Water treating method



Patented June 13, 1950 WATER TREATING METHOD William Seifrlz, Glen Riddle, and Eugene J. Mc-

Cue, Chester Springs, Pa., assignors to Edward S. Mead, Philadelphia, Pa.

No Drawing. Application July 24, 1946, Serial No. 685,920

Claims. (Cl. 21023) Our invention relates to a method of treating fluids for the removal of impurities, and more particularly to a process for treatment of water to precipitate and remove foreign matter therefrom. r

In industrial and mining operations involving the use of water for cleaning purposes in "closed systems and in systems where the emission of any eiiiuent into public streams must be freed from suspended solids, it is necessary to remove foreign matter from the water. In the latter case, sources of water supply such as rivers, streams, etc. may otherwise become polluted by the presence of such foreign matter as organic proteins.

Procedures for flocculation and removal of such matter have therefore been developed by the use of chemicals and other substances, as reagents.

In addition to the many reagents sold under various trade names, the use of starches from many sources, such as potatoes, corn, wheat, tapioca, etc. have been tried in combination with caustics prepared in many different ways and are being extensively used and recommended in the precipitation of solids from washery water in coal cleaning plants, as the most satisfactory method available at the present time even though they fall far short of desired performance due to the difilculty of maintaining a uniform flocculation, because causticized starch tends to create a slime in the settled solids which retards filtering.

In one such process employed by a large bituminous coal cleaning plant, causticized starch, two parts starch and one part sodium hydroxide, is used in the washery water, 1% solution. In this plant the total amount of washery water required for efficient washing is 1000 gallons per minute. The speed of precipitation using the starch solution is such that only 1000 gallons per minute of clean water can be obtained from an 85' settling tank with a retention time of 280 minutes. In addition to the slow rate of precipitation oi the larger particles when using the 1% solution of causticized starch, it was found that the colloidal particles were not precipitated in 280 minutes but remained in suspension leaving the water cloudy and turbid.

These limitations of starch reagents and others become more manifest as the problems of sedimentation become more difiicult because of the greater amount of foreign matter introduced into the cleaning operation because of mechanical mining and loading. In some cases the increase in solid content in washery waters is two to three times as great as heretofore.

The essence of our invention resides in a novel.

process for aggregating these particles into groups which are of relatively large size, greatly reduced total surface area, and of higher specific gravity; as a result the rate of precipitation, that is to say, the rate of settling is materially increased over the present practice.

This we effect by adding to the washery water an alkaline substance such as sodium hydroxide, calcium hydroxide, trisodium phosphate, etc., and then adding to the washery water so treated a salt of zinc, such as zinc chloride, although as will appear hereinafter, other metallic salts may be used.

Accordingly an object of our invention is to provide a novel process for the purification of water.

A further object of our invention is to reduce the total surface area through coalescence and thereby increase the size and the specific gravity of the particles, thus greatly accelerating the precipitation of impurities in coal washery water, sewage, industrial wastes, etc.

These and other objects of our invention will appear in the detailed description which follows:

Inasmuch as we have experimentally applied our invention to coal washery water, we shall describe the detailed procedure in that example. although it will be understood that the invention has application in any case where precipitation is desired.

Solids in coal washery water consist of large size particles plus 48 mesh, and these can be removed with little difllculty.

The minute colloidal particles, those among them which are protein may well be of molecular dimensions, are prevented from coalescing by their electric charge. An examination of the washery water with the ultra-microscope shows active Brownian movement of these particles.

To such washery water we admit two grains per gallon of an alkaline substance such as sodium hydroxide, calcium hydroxide, tri-sodium phosphate, etc., or suflicient to build up the pH to approximately 10.6 or over and when the washery water has been uniformly alkalized, we admit i to 2 grains of technical grade zinc chloride. Although the quantity is not critical in any pH range on the alkaline side, the speed of precipitation can be controlled by increasing the amounts a capacity of 400 gallons, and secure crystal' clear eflluent with eight minutes retention time, whereas the present methods used at the washery plant maintain 1000 gallons per minute into a tank with 280,000 gallons capacity or 280 minutes retention time, with only partial precipitation, the colloids being discharged with the added to the washery water and the pH raised to 10, we added a minut quantity of calcium hydroxide, less than 1 grain to the gallon, and then admitted 2 grains of zinc sulphate per gallon and the same results as to speed of precipitation were obtained.

' In addition, we were able to increase the speed or filtering to correspond to the speed of precipitation, whereas when the causticized starch was used alone, the speed of filtering fell far behind the speed of precipitation and made it necessary to reduce the feed to the thickening device in order to avoid building up an excess of compressed solids in the settling tank.

Although in the above we have described the use of causticized starch in solution with zinc salt, we have found that the use of starch is not necessary in th precipitation of colloidal suspensions by zinc salts.

Comparative rates of precipitation when starch is used with and without a zinc salt are given in the following experiment:

Two tests were run, each-for twelve hours. 1% solution of causticized starch (two parts starch; one part sodium hydroxide) raising the pH to 10.8 was used in the first test. In the second test-1% solution of causticized starch (two parts starch; one part sodium hydroxide) raising the pH to 10.8 plus 2 grains per gallon of zinc sulphate was used. In the first test the aggregation was slow and the fiocculated mass hung in suspension in the form of a cloud, clearing very slowly. In the second 3 test, using the zinc salt in conjunction with the causticized starch solution, the precipitation was far greater, the water clearing rapidly. The acceleration due to the zinc ion is twenty fold, the

colloidal particles even of molecular dimension Q other fields of use. Thus, further by way of example, it is possible to eliminate the use of more expensive methods of softening boiler waters by our invention. In this treatment lesser quantities of alkaline substances such as caustic soda (sodium hydroxide), tri-sodium phosphate and calcium hydroxide are used and also lesser quantitles of zinc salts thus efl'ectina' a finer flocculation which can be readily filtered out.

- It is further possible to apply our novel process for reducing the bacteria count in raw drinking water, sewage disposal eflluents, etc., by precipitating the colloidal particles which carry the bacteria. Many experiments show that raw water badly polluted and carrying a bacteria count oi 380,000 total count, 170,000 red and 100,000 B. colt after treatment with our process using '/2 grain per gallon of sodium hydroxide to raise the alkalinity to 9.8 pH and then addin ,9 grain zinc chloride and filtering, reduced the total count to less than 100 with no reds and no B. coli.

The theory of operation is as follows: three distinct processes are involved. All are familiar incolloid chemistry, but they are here combined in one method employing the most eflicient salt. Th fact that three familiar colloidal phenomena are operativ at one and the same tim accounts in major part for the efficiency of the method? and to this is to be added the emciency of the salt used. The first process bringing about sedi mentation is that of decharging the particles. This is common colloidal phenomenon. Mostcolloidal particles are negatively charged. All living cells are negatively charged and these obviously include living bacteria. Such negative particles are decharged and therefore precipitated by cations or positively charged ions such as zinc. But the precipitation is not always complete;- often the more minute of the colloidal particles are left in suspension.

It is not generally known that within a valencegroup certain ions are more eflective as precipi-- tating agents than others. Zinc, cadmium andmercury constitute a distinct group apart fromother bivalent elements such as magnesium, cal-'-' cium and barium. Why this should be true is evident from a comparison of the outer two electronic shells; each of the bivalent elements has two electrons in its outermost valence shell, but: zinc, cadmium and mercury have eighteen electrons in the next inner shell whereas the other bivalent elements have but eight electrons in the.

second inner shell.

The effect of the second electron layer onvalence is now generally recognized. The behavior of elements is in part dependent on the electronic fields around the atoms, and the in-' tensity and distribution of these fields are re-. flected in the electronegativity of the atoms. Elements with eighteen electrons in the electron orbit below the valence layer exhibit variable valence, whereas elements with eight electrons in the orbit below the outer layer have only one valence. This is why zinc, cadmium and mercury-- constitute a distinct group among the bivalent elements and ar more eflicient as precipitating 7'5-sequently, a precipitating agent which will both-'-' agents. It is this fact which has been generallyoverlooked and is embodied in our claim.

The precipitation of inorganic colloidal matter, such as the quartz particles in river water 10 sedimented by the salts of the sea, is broughtabout by decharging the particles, and this is sufllcient; but organic colloidal matter is usually hydrolyzed, th water mantle as well as the electric charge serving to stabilize the particles. Conactions; and not unless both protective layers of the organic particles in colloidal suspension are removed, that is to say, unless the particles are both decharged and dehydrated do they coalesce and fall. 1

The third process which is an essential feature of our invention is that involving a heavy flocculent precipitation produced by the interaction of the hydroxide and the metal salt. An insoluble hydroxide of the metal is produced and it comes down carrying all else with it, clearing the turbid water much in the same way that rain clears the atmosphere. This fiocculent precipitation performs the function of the starch paste sometimes used to bring down suspended colloidal matter, but it does it with much greater efficiency and greater speed than the starch paste, and avoids the slimy hard to filter" mass formed by the starch. It is in short a much cleaner as well as more effective precipitating reaction. The need of the high alkalinity is thus evident.

The above method is that best suited for clearing industrial wastes or washery water in coal cleaning or ore cleaning plants or in any situation where speed of precipitation is a vital factor. The alkalinity should be high, over 10 pH, and the salt added at least two grains per gallon. Precipitation is then rapid and complete. However, in water purification and in all situations where speed of precipitation is not an important factor, it is better to use a lower degree of alkalinity, a pH of less than 10 and a minimum salt concentration, one grain or less per gallon. F'locculation is still complete but precipitation is slow. The only disadvantage of this slower method is loss of speed of settling; however, the flocculation is complete and the fine floc" is readily filtered out, leaving the water crystal clear, as clear as before but without the excessive alkalinity and the greater amount of salt. In water purification loss of speed in settling is not important, whereas the reduction in alkalinity and the saving of salt, both from the view of cost and water taste, are very important.

Without laying undue emphasis on any one of the three types of precipitating reactions involved. it should be pointed out that the three processes take care of all possibilities. First, the larger inorganic colloidal particles are brought down by decharging; this results in coalescence, reduction in surface, increase in weight, and consequent settling. Second, as proteins are held in colloidal suspension not only by their electrical en.- vironment, whether this is a double layer or a more dispersed cloud of ions, but also by an envelope of oriented water molecules, the protein colloidal particle is both charged and hydrated. and both layers are protective. Consequently. to precipitate such protein particles they must be both decharged and dehydrated, and these are accomplished by our method. Finally, the heavy flocculate produced by the interaction of alkali and zinc or other metallic salt brings down all 8 remaining particles, in particular the very small colloidal particles which are precipitated with difficulty by salt alone.

All bacteria which adhere to the colloidal par-- ticles in suspension are also brought down as the great reduction in bacterial count shows.

The completeness of the precipitation is strikingly revealed by the great clarity of the water. Furthermore, when after the process is complete and-the water is-viewed with the ultramicroscope, it is found to be wholly free of colloidal particles in Brownian movement. Bacteria counts likewise reveal the completeness of the reaction, a reaction count of 2,500,000 per cc. taken before precipitation is reduced to 100 after precipitation.

As the interaction between the alkali and the salt is stoichiometric, this means that when both are'addedin proper proportion, they are both brought down in a changed form with the precipitate, for they are the precipitate. This means that no metallic zinc should remain in the cleared water.

The objectionable taste of sodium hydroxide is avoided by the use of calcium hydroxide.

As many washery waters, river waters which contain sewage, etc., contain large amounts of organic matter in suspension, their precipitation by zinc salts should, on the basis of the above theoretical reasoning, be more effectively brought about, and experimentation shows this to be true.

This knowledge, gained during experimental studies on flocculation, we have put to practical use in the sedimentation of coal and ore washery waters, city drinking water, etc. The ion which proved most effective in the flocculation of colloidal suspensions was zinc. 0n the basis of general colloidal principles, zinc should be no more effective than other bivalent ions, yet it is more so whether used as the chloride or the sulphate, although the chloride was found slightly more effective than the sulphate.

For most effective sedimentation, a pH of 10 or higher is best. This is true for two reasons. First, on the addition of the metallic salt a nonsoluble precipitation is formed which carries all colloidally suspended matter with it; and second,

' culating agent over other common ions is the first significant feature of our discovery, and this is supplemented by the fact that the zinc salt functions without the aid of any additional agent other than caustic soda or other alkali.

The expression industrial waste waters, as embodied in the claims, is intended to include within its scope particularly sewage eifluents as well as coal and ore washery waters, such as that resulting from coal and ore cleaning operations, but it will be understood that the generic signiflcance of the expression is not to be taken as precluding an appropriate lattitude of interpretation with respect to any industrial waste waters which are reasonably within the scope of the present invention.

Although we have herein described various applications of our invention, it will be understood that these are described only as ap lica- "Weclaim:

1. The method of removing suspended particles from an industrial waste water containing colloidal protein material which comprises addin to said industrial waste water an alkaline substance from the group consisting o1 alkali metal and alkaline earth metal compounds in an amount suiiicient to provide an alkalinity within the approximate range of pH 9 to pH 10.8, and

adding to the said waste water a zinc salt from the group consisting oi zinc chloride and zinc sulphate to form a iiocculating agent therein, thereby precipitating the suspended particles under conditions wherein they are decharged, dehydrated and coalesced.

2. The method of removing suspended particles from an industrialwaste water containing colloidal protein material which comprises adding to said solution an alkaline substance from the group consisting oi alkali metal and alkaline earth metal compounds in an amount suflicient to provide an alkalinity within the approximate range or pH 9 to pH 10.8, and adding to the industrial waste water a zinc salt from the group consisting of zinc chloride and due sulphate in the approximate amount oi between 0.5 and 2 grains per gallon of said waste water to form a flocculating agent therein substantially without unreacted zinc salt-remaining, thereby precipitating the suspended particles under conditions wherein they are decharged, dehydrated and coalesced.

3. The method of clarifying coal washery water which comprises adding to said coal washery water an alkaline substance from the group consisting of alkali metal and alkaline earth metal compounds in an amount suiiicient to provide an alkalinity within the approximate range of pH 10 to pH 10.8, and adding to the resultant washery water a zinc salt from the group consisting of zinc chloride and zinc sulfate in the approximate amount of between 1 and 2 grains per gallon of washery water to form a flocculating agent therein substantially without unreacted zinc salt remaining, thereby precipitating the suspended particles under conditions wherein they are decharged, dehydrated and coalesced.

4. The method of clarifying one washer-y wa;

ter which comprises adding to said one washery water an alkaline substance in an mount sufiicient to provide an alkalinity within the approximate range or pH 10 and pH 10.8, and

8 k addingtothewasherywaterazinosaltfrom the group consisting oi zinc chloride and flnc sulfate in an amount or approximately 1 to 2 grains per gallon of washery water to form a nocculating agent therein substantially without unreacted zinc salt remaining, thereby precipitating the suspended particles under conditions wherein they are decharged, dehydrated and coalesced.

5. The method of removing suspended particles including organic colloidal material and reducing the bacterial content in aqueous sewage disposal eiiiuents which comprises adding to said eiiiuent sodium hydroxide in an amount suilicient to provide an alkalinity of approximately pH 9.8,and adding to the eiliuent zinc chloride in the amount 01' approximately ,6 grain per gallon of eiiluent to form a iiocculating agent therein substantially without unreacted zinc chloride remaining, thereby precipitating the suspended particles and bacterial content under conditions wherein they are decharged, dehydrated and coalesced.

WILLIAM smrmz. EUGENE J. McCUE.

nnrnnnncns crrnn The following references are of record in the tile of this patent:

UNITED STATES PA'I'ENTS Number Name Date 7 668,820 Jones Feb. 26, 1901 1,757,526 Hedgpeth May 6, 1930 1,860,781 Liebknecht May 31, 1932 1,862,265 Henry June 7, 1932 1,966,733 h Reimers July 17, 1934 2,074,082 Domogalla Mar. 16, 1937 2,300,693 Oswald Nov. 3, 1942 FOREIGN PATENTS Number Country Date 17,109 Great Britain of 1895 435,126 Great Britain Sept. 16, 1935 OTHER REFERENCES Journal Chemical Society, London, vol. 127, 1925, pp. 2124-27.

Journal American Chemical society, vol. 38,

a 1916, pp. 785-788.

Journal American Leather Chemists Asso vol.

29, 1934, 1););3-18 and 52. 

1. THE METHOD OF REMOVING SUSPENDED PARTICLES FROM AN INDUSTRIAL WASTE WATER CONTAINING COLLOIDAL PROTEIN MATERIAL WHICH COMPRISES ADDING TO SAID INDUSTRIAL WASTE WATER AN ALKALINE SUBSTANCE FROM THE GROUP CONSISTING OF ALKALI METAL AND ALKALINE EACH METAL COMPOUNDS IN AN AMOUNT SUFFICIENT TO PROVIDE AN ALKALINITY WITHIN THE APPROXIMATE RANGE OF PH 9 TO PH 10.8, AND ADDING TO THE SAID WASTE WATER A ZINC SALT FROM THE GROUP CONSISTING OF ZINC CHLORIDE AND ZINC SULPHATE TO FORM A FLOCCULATING AGENT THEREIN, THEREBY PRECIPITATING THE SUSPENDED PARTICLES UNDER CONDITIONS WHEREIN THEY ARE DECHARGED, DEHYDRATED AND COALESCED. 